A Mukaiyama–Claisen Approach to 3,5-Diketo Esters

Dedicated to ‘uncle Peter’, in deep admiration for his marvelius contributions to chemical synthesis, including Synlett.

Abstract

A thermally promoted synthesis of 3,5-diketo esters via a Mukaiyama–Claisen reaction of 4H-1,3-dioxin-4-one derivatives with silyl enolates has been developed. The desired oligocarbonyl compounds were obtained with moderate to good yields.

Key words

3,5-diketo esters - Mukaiyama–Claisen reaction - thermal reaction - silylated nucleophiles

• References and Notes

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• 8 A cooling-finger-capped Schleck tube with a stirring bar was charged with the corresponding 4H-1,3-dioxin-4-one derivative 1 (0.1 mmol), silylated nucleophile 2 (0.4 mmol), and anhydrous toluene (1 mL). The resulting mixture was heated to 90 °C or 110 °C for 4–5 h until full consumption of the starting material was observed (monitored by TLC). The solvent was removed under reduced pressure, MeOH (1 mL) and KHF₂ (10 equiv) were added, and the reaction mixture was stirred at r.t. for 10 min. After filtering through a thin layer of Celite, the residue was purified by column chromatography (isohexanes–EtOAc, 5:1 to 1:1).